CN111032614A - Process for converting cyclic alkylene ureas to their corresponding alkyleneamines - Google Patents
Process for converting cyclic alkylene ureas to their corresponding alkyleneamines Download PDFInfo
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Abstract
The invention relates to a process for converting cyclic alkylene ureas to their corresponding alkylene amines, in which a feed comprising cyclic alkylene ureas is reacted in the liquid phase with water at a temperature of at least 230 ℃ in an amount of from 0 to 20mol of water per mol of urea moiety with simultaneous removal of CO2. It has been found that the process of the present invention efficiently converts alkylene ureas to the corresponding alkylene amines. The process has high yield and low by-product production. Preferred cyclic alkylene ureas include one or more of EU (ethylene urea, urea derivative of Ethylene Diamine (EDA)), UDETA (urea derivative of diethylene triamine (DETA)), UTETA (urea derivative of triethylene tetramine (TETA), DUTETA (diurea derivative of triethylene tetramine), UTEPA (urea derivative of Tetraethylenepentamine (TEPA)), DUTEPA (diurea derivative of TEPA), or pentaureaUrea derivatives of ethylene hexamine and higher analogs (PEHA), UAEEA (urea derivatives of aminoethylethanolamine), HE-UDETA (urea derivatives of hydroxyethyldiethylenetriamine), HE-UTETA (urea derivatives of hydroxyethyltriethylenetetramine), HE-DUTETA (diurea derivatives of hydroxyethyltriethylenetetramine) or any mixture of these.
Description
The present invention relates to a process for converting a cyclic alkylene urea to its corresponding alkylene amine.
Cyclic alkylene ureas are compounds that contain two nitrogen atoms connected by a carbonyl moiety and an alkylene moiety. For example, cyclic ethylene urea is a compound comprising a cyclic ethylene urea moiety in which two nitrogen atoms are connected by a carbonyl moiety and an ethylene moiety, which corresponds to the formula:
by removing the CO groups and adding two hydrogen atoms, the cyclic alkylene urea compounds can be converted into the corresponding alkylene amines. From a commercial point of view, alkylamines, in particular ethyleneamines, especially Diethylenetriamine (DETA) and higher ethyleneamines such as (linear) triethylenetetramine (L-TETA), are attractive products. Thus, cyclic ethylene ureas are attractive precursors in the preparation of ethylene diamine and higher ethylene amines.
However, it has been found that cyclic alkylene ureas are relatively stable and difficult to convert to the corresponding alkylene amines. This can also be seen from the prior art, where the conversion is carried out using a large excess of strong inorganic base or in the presence of large amounts of water. The difficulties in converting a cyclic alkyleneurea to the corresponding alkyleneamine are particularly applicable to compounds in which the alkyleneurea moiety is linked to another alkyleneamine moiety through a nitrogen atom, particularly compounds in which the alkyleneurea moiety is present between two other alkyleneamine moieties.
US4,503,250 describes a process for preparing linear polyalkylene polyamines which comprises reacting ammonia or an alkylene amine compound having two primary amino groups or a mixture thereof with an alcohol or an alkanolamine compound having primary amino groups and primary or secondary hydroxyl groups or a mixture thereof in the presence of a carbonic acid derivative at a temperature at which the reaction is carried out and under a pressure sufficient to keep the reaction mixture substantially in the liquid phase. The process results in the formation of urea adducts of polyalkylene polyamines. The urea adduct was converted to a polyethylene polyamine by reacting with 50% aqueous KOH at reflux overnight. 8 moles of KOH are used per mole of carbon dioxide.
US4,387,249 discloses the reaction of Ethylenediamine (EDA), ethanolamine (MEA) and urea to give aminoethylethyleneurea (UDETA) and Ethyleneurea (EU), which hydrolyze to form DETA and EDA. The hydrolysis step is carried out in an inert atmosphere in the presence of a bronsted base. The bronsted base is preferably an alkali metal hydroxide, more preferably an aqueous NaOH solution. In the examples, the hydrolysis was carried out at a temperature of 200 ℃ under autogenous pressure using 5 mol/l NaOH solution. The amount of NaOH used can be calculated to correspond to 6.5 moles NaOH per mole equivalent of ethylene urea moieties. It should be noted that in this reference, the compounds to be converted, i.e. aminoethylethyleneurea (UDETA) and Ethyleneurea (EU), are not difficult to convert compounds in which an alkylene urea moiety is present between two additional alkylene amine moieties.
US2,812,333 describes the simultaneous removal of CO by heating at elevated temperature in the presence of water21- (2-hydroxyethyl) imidazolidinone-2 is hydrolyzed to the corresponding hydroxyethylethylenediamine. The reaction is carried out in a large excess of water; in the examples, a 12% solution of 1- (2-hydroxyethyl) imidazolidinone-2 was used. The conversion rate is low. Under the conditions tested, approximately 5% of the compound hydrolyzed per hour.
GB878,967 points out that it is known to prepare N- β -hydroxyethylethylenediamine by hydrolysis with water in an autoclave at 175 ℃ it is not very practical to show that the process has a conversion of 25% within 8 hours.
US2,847,418 describes the hydrolysis of 1, 3-bis- (2-hydroxyethyl) -imidazolidinone-2 to the corresponding amine using a molar equivalent of 5% aqueous NaOH. The amount of water is considerable. No further information on the process conditions is provided.
There is a need in the art for a process for converting a cyclic alkylene urea to its corresponding alkylene amine that does not rely on the presence of large amounts of caustic or water and that can be carried out in an efficient manner. The present invention provides such a method.
The invention relates to a process for converting cyclic alkylene ureas to their corresponding alkylene amines, wherein a feed comprising cyclic alkylene ureas is reacted with water in the liquid phase at a temperature of at least 230 ℃ in a range of from 0.1 to 20mol water/mol waterReaction of the amount of the urea moiety with simultaneous CO removal2。
It has been found that the process of the present invention is effective in converting alkylene ureas to the corresponding alkylene amines. The process has high yield and low by-product production. In particular, it has been found that the process of the present invention, on the one hand, produces less cyclic alkylene urea as a by-product (wherein the alkylene urea moiety is present between two further alkylene amine moieties), while avoiding the use of strong bases and large amounts of aqueous solvents, thus avoiding or at least minimizing salt waste streams, corrosion and product degradation. Further advantages of the method according to the invention and its embodiments will be apparent from the further description.
The invention will be discussed in more detail below.
Figure 1 shows the chemical formulae of a number of compounds mentioned in this specification.
The starting material used in the present invention is a reaction mixture comprising a cyclic alkylene urea. Cyclic alkylene ureas are compounds that contain two nitrogen atoms connected by a carbonyl moiety and an alkylene moiety. For example, in cyclic ethylene urea, the two nitrogen atoms are connected via a carbonyl moiety and an ethylene moiety according to the formula:
in a preferred embodiment of the process of the invention, the cyclic alkylene urea is subjected to a conversion to give the corresponding alkylene amine:
wherein R is1And R2Each independently selected from hydrogen, formula X-R3-(NH-R3-)pAn alkyleneamine group of the formula X-R3-(O-R3-)nAlkoxy of (a) or a combination of the alkylene amine and alkoxy units p and N, wherein one or more units are N-R3-N-may exist as any of the following rings
And wherein each R3Independently as defined below, and X can be hydroxyl, amine, linear or branched C1-C20Hydroxyalkyl or C1-C20Aminoalkyl, n and p are independently at least 0, preferably 1-20, more preferably 2-20, optionally containing one or more piperazine, or alkyleneureido groups, or when p or n is 0, can be C1-C20Hydroxyalkyl or C1-C20Aminoalkyl, and R3Is alkylene or substituted alkylene.
In a preferred embodiment, R2Is a hydrogen atom, R1Not a hydrogen atom.
In a more preferred embodiment, R2Is a hydrogen atom, R1Is a group which may comprise repeating alkyleneamine groups, even more preferably of the formula X- (NH-C)2H4)nWherein optionally one or more-NH-C2H4the-NH-unit may be present as any of the following rings:
And wherein N is 0 to 20 and X may be a hydrogen atom, an aminoalkyl group, a hydroxyalkyl group, an N-imidazolidinone alkyl group or a piperazinoalkyl group, or when N is 0, a hydroxyalkyl group or an aminoalkyl group, most preferably wherein the alkyl group is ethyl.
R3Preferably ethylene or propylene, optionally substituted by C1-C3Alkyl substituents. More preferably, it is unsubstitutedEthyl, unsubstituted propylene or isopropylene, most preferably unsubstituted ethylene.
Some examples of the most preferred cyclic alkylene ureas are EU (ethylene urea), UDETA (urea of diethylene triamine), UTETA (urea of triethylene tetramine, i.e., U1TETA or U2TETA, depending on whether the urea is between the 1 st and 2 nd amines or between the 2 nd and 3 rd amines, respectively, in the chain), DUTETA (diurea of triethylene tetramine), UTEPA (urea of tetraethylene pentamine, i.e., U1TEPA, U2TEPA, depending on where the urea units are located), DUTEPA (DU1,3TEPA, DU1,4TEPA, diurea of tetraethylenepentamine), UAEEA (urea of aminoethylethanolamine), HE-UDETA (urea of hydroxyethyldiethylenetriamine, which may be present in two isomers HE-U1DETA and HE-U2 DETA), HE-UTETA (urea of hydroxyethyltriethylenetetramine, which may be present in three isomers HE-U1TETA, HE-U2TETA and HE-U3 TETA), HE-DUTETA (diurea of hydroxyethyltriethylenetetramine) or any mixtures of these. The molecular structure of many of the above cyclic alkylene ureas is given in figure 1. To avoid any confusion, if a number is given to the amine group on which the cyclic urea unit U is located, the amine group is counted from the terminal amine group on the molecule, which in the case of hydroxyethylated ethyleneamines is an amine group that does not contain a hydroxyl group at the terminal.
The process of the invention is particularly suitable for converting alkylene amine mixtures comprising at least 10 mol% of a compound containing-NH-R3-NH-R3-NH-R3-a cyclic urea derivative of an alkylene amine compound of the NH-moiety, calculated on the total amount of cyclic urea compound present in the mixture. Cyclic urea derivatives of compounds having such moieties are relatively difficult to convert to the corresponding amines and a feature of the process of the invention is that mixtures comprising these compounds can be converted while obtaining high yields. It may be preferred that the starting material is an alkylene amine mixture comprising at least 15 mol%, in particular at least 20 mol%, of-NH-R-containing compounds3-NH-R3-NH-R3-a cyclic urea derivative of an alkylene amine compound of the NH-moiety, calculated on the total amount of cyclic urea compound present in the mixture.
In the process of the present invention, it is preferred,reacting a feed comprising cyclic alkylene urea in the liquid phase with water in an amount of 0.1-20 moles water per mole urea moiety at a temperature of at least 230 ℃ with CO removal2。
In the process of the present invention, water is used in an amount of from 0.1 to 20 moles of water per mole of urea moiety present in the starting feed. The range of 0.1 to 20 moles of water per mole of urea moieties refers to the total amount of water added during the process, calculated on the amount of urea moieties in the feed at the start of the reaction. To achieve complete conversion, 1 mole of water is required per mole of urea moiety to be converted. Since complete conversion is not always necessary, smaller amounts of water can be used. Thus, the amount of water is at least 0.1 mole per mole of urea moiety. Higher amounts are generally used, for example at least 0.2 mole per mole of urea moiety, in particular at least 0.5 mole of water per mole of urea moiety.
It has been found that in the process of the invention, good conversions can be obtained with a relatively limited amount of water (up to 20 moles of water per mole of urea moiety). It has been found that it is possible to work with even lower amounts of water, for example amounts of up to 15 moles of water per mole of urea moieties, more particularly amounts of up to 10 moles of water per mole of urea moieties, or even amounts of up to 5 moles of water per mole of urea moieties.
Preferably, the composition provided to the first step consists of at least 70% by weight of cyclic alkylene urea, especially those described as preferred above, and, if present, an amine compound selected from the group consisting of primary, cyclic secondary and bicyclic tertiary amines, especially those described as preferred above, based on the total water amount. It is particularly preferred that the composition provided to the first step represents at least 80% by weight, more particularly at least 90% by weight, of the total amount of these compounds.
The water may be added at the start of the process in a single shot. However, it is preferred to add the water in several charges or continuously during the process. In continuous operation, multiple feed points may be used. By matching the amount of water added to the amount of water consumed by the reaction, the excess water in the reaction mixture can be limited. This has been found to limit the formation of by-products.
The molar ratio of water to urea moieties is calculated based on the water present in the liquid reaction medium. If water is added in the form of steam (which may be an attractive embodiment of adding water in combination with providing heat to the reaction mixture), a large portion of the water in the steam will not be absorbed in the liquid reaction medium. The conditions for adjusting the water addition process by steam in such a way that the desired amount of water is absorbed by the reaction medium are within the scope of the skilled person. Water may also be present in the feed from the start of the reaction, for example as a result of the process used to prepare the feed. Water may also be added as a liquid.
The reaction is carried out at a temperature of at least 230 ℃. It has been found that at temperatures below this value the reaction rate is too low to obtain a meaningful conversion within an acceptable time frame. The reaction is preferably carried out at a temperature of at least 240 c, in particular at least 250 c. As maximum values, mention may be made of values of 400 ℃. It may be preferred to carry out the reaction at a temperature of at most 350 c, in particular at most 320 c.
The pressure in the process is not critical as long as the reaction medium is in the liquid phase. As a general range, values of from 0.5 to 100 bar may be mentioned, depending on the desired temperature. Preferably CO2The removal step is carried out at a pressure of at least 5 bar, in particular at least 10 bar, so as to maintain a sufficient amount of amine and water in the medium. In view of the high costs associated with high pressure devices, the pressure may preferably be at most 50 bar, in particular at most 40 bar.
CO removal in the process of the invention2. When the conversion of the alkylene urea to the ethyleneamine compound is complete, CO may proceed2And (4) removing. However, it is preferred to carry out the CO during the reaction2And (4) removing. CO 22Removal may be performed in a manner known in the art. The most basic method of doing so is to vent the reaction vessel. Stripping fluids, especially stripping gases, can be used to increase CO2And (4) removing rate. Other improved CO2Measures for removal are known to those skilled in the art and include such measures as stirring the reaction mixture, sparging of stripping gas, thin film evaporation, use of packing or trays, and the like.
In the case of stripping gas, the flow rate is generally at least 1m3/1m3Reactor volume hour (at reaction temperature and pressure) and up to 100m3/1m3Reactor volume hour (at reaction temperature and pressure). The stripping flow rate may be generated by evaporation of a liquid within the reactor vessel, resulting in the in situ generation of a stripping gas. The above ranges also apply to the present embodiment. Of course, it is also possible to combine the addition of stripping gas with the in situ formation of stripping gas.
From CO2CO-containing gas removed in the removing step2The stripping fluid of (A) may for example comprise from 1 to 99 mol% CO2. In other embodiments, the stripping fluid may comprise 1 to 80 mol% CO2Or 1 to 60 mol% CO2. In some embodiments, CO2The effluent of the removal step may contain 1-40 mol% CO2Or 1-20 mol% CO2. Lower CO2The content favors more efficient stripping, but it is also advantageous to use more stripping gas. It is within the purview of one skilled in the art to find an appropriate balance between these parameters.
The reaction time can vary within wide limits, for example at least 1 minute, in particular at least 5 minutes, more in particular from 15 minutes to 24 hours, depending on the reaction temperature and the desired degree of conversion. In one embodiment, the reaction time may be at least 30 minutes, or at least 1 hour. It may be preferred that the reaction time preferably varies between 1 hour and 12 hours, in particular between 1 hour and 6 hours. When lower temperatures are used, longer reaction times may be required to achieve the desired degree of conversion.
The process of the present invention does not rely on the use of strong inorganic bases. However, if desired, a limited amount of a strong inorganic base may be present. In the context of the present invention, a strong inorganic base is a substance which does not contain a carbon-carbon bond and has a pKb of less than 1. In one embodiment, if an inorganic strong base is used, it is selected from metal hydroxides, in particular from hydroxides of alkali metals and alkaline earth metals, in particular from sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide and barium hydroxide. In one embodiment, the inorganic strong base is selected from metal oxides, in particular from oxides of alkali metals and alkaline earth metals, in particular from calcium oxide, magnesium oxide and barium oxide. It may be preferred to select the inorganic strong base from sodium hydroxide, potassium hydroxide, magnesium (hydr) oxide and calcium (hydr) oxide. It can be seen as particularly preferred to use sodium hydroxide and potassium hydroxide. Other strong inorganic bases, such as ammonium hydroxide, may also be used. Mixtures of various inorganic strong bases may be used, as known to those skilled in the art. In addition to other components, compounds containing strong bases, which can be converted in the reaction medium into compounds of inorganic strong bases, can also be used. If a strong inorganic base is used, it is generally used in an amount of less than 0.5 mole of inorganic base per mole of cyclic alkylene urea moiety, in particular less than 0.2 mole of inorganic base per mole of cyclic alkylene urea moiety.
In one embodiment of the invention, the process of the invention is carried out in the presence of an amine compound selected from primary amines, cyclic secondary amines and bicyclic tertiary amines. It has been found that an increased reaction rate can be obtained.
The primary amine being one in which the amine group has the formula R4-NH2In which R is4Can be any organic group, preferably an aliphatic hydrocarbon with optional heteroatoms such as oxygen and/or nitrogen. The cyclic secondary amine is of the formula R5-NH-R6Wherein R is5And R6Together form a hydrocarbon ring, optionally with heteroatoms such as oxygen and/or nitrogen, preferably a piperazine ring. Bicyclic tertiary amines of formula R7-N(-R9)-R8Wherein R is7And R8Together form a hydrocarbon ring optionally having heteroatoms such as oxygen and/or nitrogen, and R7And R9Together form another hydrocarbon ring optionally having heteroatoms such as oxygen and/or nitrogen. On all the above-mentioned groups, substituents R may be present4To R9Such as alkyl or hydroxyalkyl. Primary, cyclic secondary and bicyclic tertiary amines all contain sterically relatively unhindered amine groups. In this context, if one amine group in a compound is a primary or cyclic secondary or bicyclic tertiary amine group, the compound is defined as a primary or cyclic secondary or bicyclic tertiary amine group and is reacted withWhether or not the compound contains other amine groups which may differ in nature. The compounds may also contain two or more different amine functions, such as primary and cyclic secondary amine functions or primary, cyclic secondary and bicyclic tertiary amine functions.
Preferred examples of primary amines are alkylamines, linear ethyleneamines and alkanolamines. Preferred examples of cyclic secondary amines are amines containing a terminal piperazine ring. Preferred examples of bicyclic tertiary amines are 1, 4-diazabicyclo [2.2.2] octane (DABCO), 1, 4-diazabicyclo [2.2.2] octan-2-yl-methanol and 1-azabicyclo [2.2.2] octane (quinuclidine).
The amine compound is preferably a compound having more than one amine group, wherein at least one amine group is a primary amine, even more preferably it is an amine wherein two amine groups are primary amines. The amine compound is preferably different from R1-NH-R3-NH-R2The compound of (1), which is obtained by the process of the present invention.
In another preferred embodiment, the amine compound is a compound that can bind to the carbonyl group of the cyclic ethylene urea. Preferred amine compounds include alkyleneamine or alkanolamine compounds, even more preferably, lower alkyleneamines, ethyleneamines or alkanolamines, ethanolamines than are formed by the process of the present invention, most preferably Ethylenediamine (EDA), Diethylenetriamine (DETA), Monoethanolamine (MEA), aminoethylethanolamine (AEEA), N-Aminoethylpiperazine (AEP), N '-Diaminoethylpiperazine (DAEP), UDETA, N' -diaminoethyl-2-imidazolidinone (U2TETA), tris-aminoethylamine (TAEA).
In a further preferred embodiment, the amine compound is a compound which binds to the carbonyl group of the cyclic alkylene urea to give, inter alia, other linear or cyclic alkylene ureas or linear or cyclic alkylene carbamates, which are more or less volatile than the alkylene amine formed by the process of the present invention, even more preferably an ethylene amine which is solid under the conditions used for working up the reaction mixture or an ethylene amine bound to a solid support. Examples are DETA-PS (i.e. diethylenetriamine linked to solid polystyrene) or solid Polyethyleneimine (PEI).
CO which can be used in the process of the invention2In the removal stepPreferred amine compounds include Ethylenediamine (EDA), N-methylethylenediamine (MeEDA), Diethylenetriamine (DETA), ethanolamine (MEA), aminoethylethanolamine (AEEA), piperazine (PIP), N-Aminoethylpiperazine (AEP), 1, 4-diazabicyclo [2.2.2] on a solid support]Octane (DABCO), 1, 4-diazabicyclo [2.2.2]Octane-2-yl-methanol, triethylenetetramine (TETA), N-diethyldiamine-2-imidazolidinone (U1TETA), N' -Diaminoethylpiperazine (DAEP), N- [ (2-aminoethyl) 2-aminoethyl]Piperazine) (PEEDA), the cyclic Urea of PEEDA (UPEEDA), N' -diaminoethyl-2-imidazolidinone (U2TETA), Tetraethylenepentamine (TEPA), Pentaethylenehexamine (PEHA), and the monocyclic ureas of TEPA and PEHA (i.e., U1TEPA, U2TEPA, U1PEHA, U2PEHA, U3PEHA) and the bicyclic urea isomer of PEHA (i.e., DUPEHA), Polyethyleneimine (PEI) or alkyleneamines.
If an amine compound is used, it is metered in a molar amount of preferably 0.001 to 100 equivalents, more preferably 0.01 to 50 equivalents, even more preferably 0.05 to 30 equivalents, still more preferably 0.15 to 25 equivalents, most preferably 0.20 to 20 equivalents, relative to the total molar amount of the cyclic ethylene urea.
The process of the present invention results in the formation of a reaction mixture comprising an alkylene amine, preferably an ethylene amine.
The process of the present invention may be carried out in a batch operation, a batch feed operation or a continuous operation, for example in a cascaded continuous flow reactor. Depending on the scale of operation, continuous operation may be preferred.
The invention is illustrated by the following examples without being restricted thereto or thereby.
Example 1: conversion of DUTETA at a 4:1 ratio of water to urea
The experimental set-up used in the experiments described below was a 2000ml volume pressure vessel equipped with a condenser, pressure regulator, gas distributor and mixer. The pressure in the reaction vessel and the condenser was kept constant at 30 bar (absolute) using a pressure regulator. The top temperature of the condenser was maintained between 30-60 ℃. During the reaction, the mixture was continuously stirred and a constant flow of N2 gas was supplied to the reactor vessel using a gas distributor. Gases or vapours above 30 bar (absolute) which are produced or fed into the system during the reaction are allowed to escape from the reactor through the condenser and the pressure regulator.
The reaction mixture was prepared by mixing 430g of DUTETA and 300g H2O. The molar ratio of H2O to urea moieties was 4: 1. The mixture was kept in the above reactor at 270 ℃ for 5.4 hours. N used2The gas flow rate was 2L/min. Gas chromatography analysis using a flame ionization detector (GC-FID analysis) showed that the conversion of DUTETA to L-TETA was 54% and 70% of the initial urea groups were removed from the system. CO 22The removal rate of (A) was 0.54 mol/kg/hr.
This example shows that DUTETA can be converted to L-TETA in the presence of a limited amount of water.
Examples 2 to 4: conversion of DUTETA at different water to urea ratios
Example 1 was repeated in the same experimental setup with different water to urea ratios. The reaction time was chosen in each experiment so that the removal rate could be calculated with reasonable accuracy. The results are shown in Table 1.
TABLE 1
In table 1, examples 1, 2 and 3 are according to the invention. They show that operating at water to urea moiety molar ratios of 4:1, 10:1 and 1:1 results in substantial removal of the urea groups with good selectivity to L-TETA. Contrary to expectations, more water (H) was present in comparative example 42An O/U molar ratio of 50:1) results in a lower selectivity for L-TETA and also in a lower removal rate.
Example 5: conversion of UDETA at a 4:1 ratio of water to urea
In the experimental setup as described in example 1, 350g of UDETA and 191g H were mixed2O to prepare a reaction mixture. H2The molar ratio of O to urea moieties was 4: 1. The mixture was kept in the above reactor at 270 ℃ for 5.8 hours. N used2The gas flow rate was 4L/min.Gas chromatography analysis using a flame ionization detector (GC-FID analysis) showed that the conversion of UDETA to DETA was 55% and 60% of the initial urea groups were removed from the system. The average removal rate was 0.62 mol/kg/hour.
Example 6: conversion of UAEEA at a 4:1 ratio of water to Urea
In the experimental setup as described in example 1, 350g of UAEEA and 188g H were mixed2O to prepare a reaction mixture. H2The molar ratio of O to urea moieties was 4: 1. The mixture was kept in the above reactor at 250 ℃ for 4.2 hours. N used2The gas flow rate was 2L/min.
Gas chromatography analysis using a flame ionization detector (GC-FID analysis) showed 42% conversion of UAEEA to AEEA and 38% of the initial urea groups were removed from the system. The average removal rate was 0.45 mol/kg/hour.
Example 7: conversion of UAEEA at a water to urea ratio of 0.5:1
In the experimental setup as described in example 1, 500g of UAEEA and 33g H were mixed2O to prepare a reaction mixture. H2The molar ratio of O to urea moieties was 0.5: 1. The mixture was kept in the above reactor at 250 ℃ for 4.25 hours. N used2The gas flow rate was 1.5L/min. Gases or vapours above 20 bar (absolute) which are produced or added to the system during the reaction are allowed to escape from the reactor through the condenser and the pressure regulator.
Gas chromatography analysis using a flame ionization detector (GC-FID analysis) showed 13% conversion of UAEEA to AEEA and 13% of the initial urea groups were removed from the system. The average removal rate was 0.23 mol/kg/hour.
Claims (11)
1. Process for converting cyclic alkylene ureas to their corresponding alkylene amines, in which a feed comprising cyclic alkylene ureas is reacted in the liquid phase with water at a temperature of at least 230 ℃ in an amount of from 0.1 to 20mol of water per mol of urea moiety with simultaneous removal of CO2。
2. A process according to claim 1, wherein the cyclic alkylene urea is reacted to alkylene amine according to the following reaction:
wherein R is1And R2Each independently selected from hydrogen, formula X-R3-(NH-R3-)pAn alkyleneamine group of the formula X-R3-(O-R3-)nAlkoxy of (a), or a combination of the alkylene amine and alkoxy units p and N, wherein optionally one or more units-N-R3-N-may exist as any of the following rings:
And wherein each R3Independently as defined below, and X can be hydroxyl, amine, straight or branched C1-C20Hydroxyalkyl or C1-C20Aminoalkyl, n and p are independently at least 1, preferably 2-20, optionally containing one or more piperazine, or alkyleneureido groups, or when p or n is 0, it may be C1-C20Hydroxyalkyl or C1-C20Aminoalkyl, and R3Is alkylene or substituted alkylene.
3. The method according to claim 2, wherein R2Is a hydrogen atom.
4. A process according to claim 2 or 3, wherein R is3Ethylene, propylene or isopropylene, in particular ethylene.
5. The process according to any one of the preceding claims, wherein the cyclic alkylene ureas comprise one or more EU (ethylene urea, urea derivative of Ethylene Diamine (EDA)), UDETA (urea derivative of diethylene triamine (DETA)), UTETA (urea derivative of triethylene tetramine (TETA), DUTETA (diurea derivative of triethylene tetramine), UTEPA (urea derivative of Tetraethylpentamine (TEPA)), DUTEPA (diurea derivative of TEPA) or pentaethylene hexamine (PEHA) and higher analogues, UAEEA (urea derivative of aminoethylethanolamine), HE-UDETA (urea derivative of hydroxyethyldiethylene triamine), HE-UTETA (urea derivative of hydroxyethyltriethylene tetramine), HE-DUTETA (diurea derivative of hydroxyethyltriethylene tetramine), or any mixture of these.
6. The process according to any one of the preceding claims, wherein the feed comprises at least 10 mol%, in particular at least 15 mol%, more in particular at least 20 mol% of a compound comprising-NH-R3-NH-R3-NH-R3-a cyclic urea derivative of an alkylene amine compound of the NH-moiety, calculated on the total amount of cyclic urea compound present in the mixture.
7. The process according to any one of the preceding claims, wherein the molar ratio of water to urea moieties is at most 15 moles of water per mole of urea moieties, more particularly at most 10 moles of water per mole of urea moieties, or even at most 5 moles of water per mole of urea moieties.
8. The process according to any of the preceding claims, wherein water is added in several charges or continuously during the process.
9. The process according to any one of the preceding claims, wherein the reaction is carried out at a temperature of at least 240 ℃, in particular at least 250 ℃ and preferably at most 400 ℃, in particular at most 350 ℃, more in particular at most 320 ℃.
10. The process according to any of the preceding claims, wherein CO is removed during the reaction2。
11. The process according to any one of the preceding claims, wherein the reaction is carried out for a reaction time of from 15 minutes to 24 hours, in particular from 1 to 12 hours, more in particular from 1 to 6 hours.
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EP17185949.9 | 2017-08-11 | ||
EP17185949 | 2017-08-11 | ||
PCT/EP2018/071321 WO2019030192A1 (en) | 2017-08-11 | 2018-08-07 | Process for converting cyclic alkyleneureas into their corresponding alkyleneamines |
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US (1) | US10793511B2 (en) |
EP (1) | EP3665150A1 (en) |
JP (2) | JP2020529454A (en) |
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CN110072838B (en) * | 2016-12-15 | 2022-04-15 | 阿克苏诺贝尔化学品国际有限公司 | Process for preparing ethyleneamines |
US10995058B2 (en) | 2016-12-15 | 2021-05-04 | Nouryon Chemicals International B.V. | Process for manufacturing hydroxyethyl ethylene amines |
WO2019011710A1 (en) * | 2017-07-10 | 2019-01-17 | Akzo Nobel Chemicals International B.V. | Process to prepare ethylene amines and ethylene amine derivatives |
EP3665152A1 (en) * | 2017-08-11 | 2020-06-17 | Nouryon Chemicals International B.V. | Process for converting cyclic alkylene ureas into their corresponding alkylene amines |
MX2020001448A (en) * | 2017-08-11 | 2020-07-13 | Nouryon Chemicals Int Bv | Process to convert the cyclic monourea of an ethylene amine compound into the ethylene amine compound. |
US11685673B2 (en) | 2021-06-06 | 2023-06-27 | Christopher R. Moylan | Systems and methods for removal of carbon dioxide from seawater |
US11407667B1 (en) | 2021-06-06 | 2022-08-09 | Christopher R. Moylan | Systems and methods for removal of carbon dioxide from seawater |
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CN111032614B (en) | 2023-04-11 |
KR20200036926A (en) | 2020-04-07 |
BR112020002460B1 (en) | 2023-03-21 |
TWI761571B (en) | 2022-04-21 |
BR112020002460A2 (en) | 2020-07-28 |
US10793511B2 (en) | 2020-10-06 |
US20200199060A1 (en) | 2020-06-25 |
EP3665150A1 (en) | 2020-06-17 |
TW201920066A (en) | 2019-06-01 |
JP2023022000A (en) | 2023-02-14 |
MX2020001592A (en) | 2020-07-21 |
WO2019030192A1 (en) | 2019-02-14 |
JP2020529454A (en) | 2020-10-08 |
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